US20090093628A1 - Process for Production of Amides or Lactams - Google Patents
Process for Production of Amides or Lactams Download PDFInfo
- Publication number
- US20090093628A1 US20090093628A1 US12/224,660 US22466007A US2009093628A1 US 20090093628 A1 US20090093628 A1 US 20090093628A1 US 22466007 A US22466007 A US 22466007A US 2009093628 A1 US2009093628 A1 US 2009093628A1
- Authority
- US
- United States
- Prior art keywords
- group
- formula
- oxime
- represented
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000003951 lactams Chemical class 0.000 title claims abstract description 36
- 150000001408 amides Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- -1 oxime compound Chemical class 0.000 claims abstract description 101
- 150000001298 alcohols Chemical class 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 31
- 239000000470 constituent Substances 0.000 claims abstract description 27
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 125000005843 halogen group Chemical group 0.000 claims abstract description 25
- 125000000962 organic group Chemical group 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008707 rearrangement Effects 0.000 claims abstract description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052705 radium Inorganic materials 0.000 claims description 14
- 229910052701 rubidium Inorganic materials 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 66
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 60
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 238000003756 stirring Methods 0.000 description 31
- 125000001424 substituent group Chemical group 0.000 description 29
- 239000007789 gas Substances 0.000 description 25
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 21
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 17
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 17
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 17
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 15
- 238000006462 rearrangement reaction Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 238000004587 chromatography analysis Methods 0.000 description 14
- 125000001153 fluoro group Chemical group F* 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 125000004438 haloalkoxy group Chemical group 0.000 description 12
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 description 11
- 150000003918 triazines Chemical class 0.000 description 11
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 150000002832 nitroso derivatives Chemical class 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 150000002923 oximes Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003216 pyrazines Chemical class 0.000 description 6
- 150000004892 pyridazines Chemical class 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N CC(C)C Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 5
- GPASKFIFXOCRNP-UHFFFAOYSA-N CN=C(C)C Chemical compound CN=C(C)C GPASKFIFXOCRNP-UHFFFAOYSA-N 0.000 description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- SCRFXJBEIINMIC-UHFFFAOYSA-N n-cyclododecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCC1 SCRFXJBEIINMIC-UHFFFAOYSA-N 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 5
- 150000003230 pyrimidines Chemical class 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- QYJXLOJGVNOMNT-UHFFFAOYSA-N 2,4,6-tris(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1,3,5-triazine Chemical compound FC(F)(F)C(C(F)(F)F)OC1=NC(OC(C(F)(F)F)C(F)(F)F)=NC(OC(C(F)(F)F)C(F)(F)F)=N1 QYJXLOJGVNOMNT-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- QIMJKZDKTQAIKO-UHFFFAOYSA-N C.C=NC Chemical compound C.C=NC QIMJKZDKTQAIKO-UHFFFAOYSA-N 0.000 description 3
- BEUFFTIDRVXJKX-UHFFFAOYSA-N C.C=NO Chemical compound C.C=NO BEUFFTIDRVXJKX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N CC(C)O Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYAWQGFWGRLSON-UHFFFAOYSA-N CN=C([Rb])[RaH] Chemical compound CN=C([Rb])[RaH] FYAWQGFWGRLSON-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NQJJJEAWHUJGKL-UHFFFAOYSA-N ON=C([Rb])[RaH] Chemical compound ON=C([Rb])[RaH] NQJJJEAWHUJGKL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VZZLJYVTLHXNHC-UHFFFAOYSA-N n-[[4,6-bis[(cyclododecylideneamino)oxy]-1,3,5-triazin-2-yl]oxy]cyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=NC(ON=C2CCCCCCCCCCC2)=NC(ON=C2CCCCCCCCCCC2)=N1 VZZLJYVTLHXNHC-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000009935 nitrosation Effects 0.000 description 3
- 238000007034 nitrosation reaction Methods 0.000 description 3
- 125000006574 non-aromatic ring group Chemical group 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- JPMHUDBOKDBBLG-UHFFFAOYSA-N 3,3,4,4,4-pentafluorobutan-1-ol Chemical compound OCCC(F)(F)C(F)(F)F JPMHUDBOKDBBLG-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- OENGSNXUALAIFP-UHFFFAOYSA-N n-cycloheptylidenehydroxylamine Chemical compound ON=C1CCCCCC1 OENGSNXUALAIFP-UHFFFAOYSA-N 0.000 description 2
- KTPUHSVFNHULJH-UHFFFAOYSA-N n-cyclooctylidenehydroxylamine Chemical compound ON=C1CCCCCCC1 KTPUHSVFNHULJH-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 description 1
- VTWKXBJHBHYJBI-VURMDHGXSA-N (nz)-n-benzylidenehydroxylamine Chemical compound O\N=C/C1=CC=CC=C1 VTWKXBJHBHYJBI-VURMDHGXSA-N 0.000 description 1
- FWSXGNXGAJUIPS-WAYWQWQTSA-N (nz)-n-pentan-2-ylidenehydroxylamine Chemical compound CCC\C(C)=N/O FWSXGNXGAJUIPS-WAYWQWQTSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- QVXZSAWOXGFNIK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropan-2-ol Chemical compound FC(F)(F)C(F)(O)C(F)(F)F QVXZSAWOXGFNIK-UHFFFAOYSA-N 0.000 description 1
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- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- SMTWDFISDOTPCZ-UHFFFAOYSA-N cyclononadecane Chemical compound C1CCCCCCCCCCCCCCCCCC1 SMTWDFISDOTPCZ-UHFFFAOYSA-N 0.000 description 1
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 1
- JNFIMRWCDIOUMT-UHFFFAOYSA-N cyclooctadecane Chemical compound C1CCCCCCCCCCCCCCCCC1 JNFIMRWCDIOUMT-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- SRONXYPFSAKOGH-UHFFFAOYSA-N cyclopentadecane Chemical compound C1CCCCCCCCCCCCCC1 SRONXYPFSAKOGH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- KATXJJSCAPBIOB-UHFFFAOYSA-N cyclotetradecane Chemical compound C1CCCCCCCCCCCCC1 KATXJJSCAPBIOB-UHFFFAOYSA-N 0.000 description 1
- UEVXKGPJXXDGCX-UHFFFAOYSA-N cyclotridecane Chemical compound C1CCCCCCCCCCCC1 UEVXKGPJXXDGCX-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- SGRWGISGVDVSJV-UHFFFAOYSA-N hexyl nitrite Chemical compound CCCCCCON=O SGRWGISGVDVSJV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- APNSGVMLAYLYCT-UHFFFAOYSA-N isobutyl nitrite Chemical compound CC(C)CON=O APNSGVMLAYLYCT-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- YGZXYVKELHQDAJ-UHFFFAOYSA-N n-(1,3,5-triazin-2-yloxy)cyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=NC=NC=N1 YGZXYVKELHQDAJ-UHFFFAOYSA-N 0.000 description 1
- XAMCVQOOVOEXKL-UHFFFAOYSA-N n-(1,3,5-triazin-2-yloxy)cyclohexanimine Chemical compound C1CCCCC1=NOC1=NC=NC=N1 XAMCVQOOVOEXKL-UHFFFAOYSA-N 0.000 description 1
- FNMOWADXAAVOPW-UHFFFAOYSA-N n-(1-cyclohexylpropylidene)hydroxylamine Chemical compound CCC(=NO)C1CCCCC1 FNMOWADXAAVOPW-UHFFFAOYSA-N 0.000 description 1
- SPFKYSMRVBBUBO-UHFFFAOYSA-N n-[(4-chloro-1,3,5-triazin-2-yl)oxy]cyclododecanimine Chemical compound ClC1=NC=NC(ON=C2CCCCCCCCCCC2)=N1 SPFKYSMRVBBUBO-UHFFFAOYSA-N 0.000 description 1
- PMFKYFWQCSHCIA-UHFFFAOYSA-N n-[(4-chloro-1,3,5-triazin-2-yl)oxy]cyclohexanimine Chemical compound ClC1=NC=NC(ON=C2CCCCC2)=N1 PMFKYFWQCSHCIA-UHFFFAOYSA-N 0.000 description 1
- AKNLJZYWGMYRTB-UHFFFAOYSA-N n-[2-(cyclododecylideneamino)oxypyrimidin-4-yl]oxycyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=CC=NC(ON=C2CCCCCCCCCCC2)=N1 AKNLJZYWGMYRTB-UHFFFAOYSA-N 0.000 description 1
- UUJFUBPODAWEIS-UHFFFAOYSA-N n-[[4,6-bis(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1,3,5-triazin-2-yl]oxy]cyclododecanimine Chemical compound FC(F)(F)C(C(F)(F)F)OC1=NC(OC(C(F)(F)F)C(F)(F)F)=NC(ON=C2CCCCCCCCCCC2)=N1 UUJFUBPODAWEIS-UHFFFAOYSA-N 0.000 description 1
- HQLPSCNGBCHXLB-UHFFFAOYSA-N n-[[4,6-bis(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1,3,5-triazin-2-yl]oxy]cyclohexanimine Chemical compound FC(F)(F)C(C(F)(F)F)OC1=NC(OC(C(F)(F)F)C(F)(F)F)=NC(ON=C2CCCCC2)=N1 HQLPSCNGBCHXLB-UHFFFAOYSA-N 0.000 description 1
- UEWYWWKEGLOACU-UHFFFAOYSA-N n-[[4,6-bis[(cyclohexylideneamino)oxy]-1,3,5-triazin-2-yl]oxy]cyclohexanimine Chemical compound C1CCCCC1=NOC1=NC(ON=C2CCCCC2)=NC(ON=C2CCCCC2)=N1 UEWYWWKEGLOACU-UHFFFAOYSA-N 0.000 description 1
- CGDHRYSILYEUES-UHFFFAOYSA-N n-[[4-(cyclododecylideneamino)oxy-1,3,5-triazin-2-yl]oxy]cyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=NC=NC(ON=C2CCCCCCCCCCC2)=N1 CGDHRYSILYEUES-UHFFFAOYSA-N 0.000 description 1
- SOLVCDOOEYGTJV-UHFFFAOYSA-N n-[[4-(cyclohexylideneamino)oxy-1,3,5-triazin-2-yl]oxy]cyclohexanimine Chemical compound C1CCCCC1=NOC1=NC=NC(ON=C2CCCCC2)=N1 SOLVCDOOEYGTJV-UHFFFAOYSA-N 0.000 description 1
- KSZLTWCWRCOHSK-UHFFFAOYSA-N n-[[4-chloro-6-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1,3,5-triazin-2-yl]oxy]cyclododecanimine Chemical compound FC(F)(F)C(C(F)(F)F)OC1=NC(Cl)=NC(ON=C2CCCCCCCCCCC2)=N1 KSZLTWCWRCOHSK-UHFFFAOYSA-N 0.000 description 1
- VFVKEXAVZDKRQW-UHFFFAOYSA-N n-[[4-chloro-6-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)-1,3,5-triazin-2-yl]oxy]cyclohexanimine Chemical compound FC(F)(F)C(C(F)(F)F)OC1=NC(Cl)=NC(ON=C2CCCCC2)=N1 VFVKEXAVZDKRQW-UHFFFAOYSA-N 0.000 description 1
- DNYZBFWKVMKMRM-UHFFFAOYSA-N n-benzhydrylidenehydroxylamine Chemical compound C=1C=CC=CC=1C(=NO)C1=CC=CC=C1 DNYZBFWKVMKMRM-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- YDYCXDWUKJSHMI-UHFFFAOYSA-N n-cyclobutylidenehydroxylamine Chemical compound ON=C1CCC1 YDYCXDWUKJSHMI-UHFFFAOYSA-N 0.000 description 1
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- DBAFMGRTCBZICI-UHFFFAOYSA-N n-cyclononylidenehydroxylamine Chemical compound ON=C1CCCCCCCC1 DBAFMGRTCBZICI-UHFFFAOYSA-N 0.000 description 1
- BLYAPMAEKUKPHC-UHFFFAOYSA-N n-cyclooctadecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCCCCCCCC1 BLYAPMAEKUKPHC-UHFFFAOYSA-N 0.000 description 1
- MIMLVMHHSQXPAY-UHFFFAOYSA-N n-cyclopentadecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCCCCC1 MIMLVMHHSQXPAY-UHFFFAOYSA-N 0.000 description 1
- BNVLIKHTHIFMNV-UHFFFAOYSA-N n-cyclopropylidenehydroxylamine Chemical compound ON=C1CC1 BNVLIKHTHIFMNV-UHFFFAOYSA-N 0.000 description 1
- ZLNMTHAAACVGRM-UHFFFAOYSA-N n-cyclotetradecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCCCC1 ZLNMTHAAACVGRM-UHFFFAOYSA-N 0.000 description 1
- SSZUPSDXTFXCLS-UHFFFAOYSA-N n-cyclotridecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCCC1 SSZUPSDXTFXCLS-UHFFFAOYSA-N 0.000 description 1
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical compound CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 1
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 1
- PPEANXDAKYECEV-UHFFFAOYSA-N n-pyrazin-2-yloxycyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=CN=CC=N1 PPEANXDAKYECEV-UHFFFAOYSA-N 0.000 description 1
- GRIZEAYILQVZFM-UHFFFAOYSA-N n-pyridazin-3-yloxycyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=CC=CN=N1 GRIZEAYILQVZFM-UHFFFAOYSA-N 0.000 description 1
- WMVMSSSAICEYMG-UHFFFAOYSA-N n-pyridin-2-yloxycyclododecanimine Chemical compound C1CCCCCCCCCCC1=NOC1=CC=CC=N1 WMVMSSSAICEYMG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- AFLQDEOAJRGCOW-UHFFFAOYSA-N nitrosocyclohexane Chemical compound O=NC1CCCCC1 AFLQDEOAJRGCOW-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HTIXSIBTBYVJHX-UHFFFAOYSA-N phenyl nitrite Chemical compound O=NOC1=CC=CC=C1 HTIXSIBTBYVJHX-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- HHIMNFJHTNVXBJ-UHFFFAOYSA-L zinc;dinitrite Chemical compound [Zn+2].[O-]N=O.[O-]N=O HHIMNFJHTNVXBJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
- C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
Definitions
- the present invention relates to processes for the production of lactams or amides that are useful typically as raw materials for pharmaceutical drugs, agricultural chemicals, dyestuffs, polyamides and the like, or as solvents. More specifically, it relates to processes for producing the amides or lactams through rearrangement reactions of oxime compounds.
- Non-patent Document 1 J. AM. CHEM. SOC. 2005, 127, 11240-11241
- An object of the present invention is to provide a process that allows a rearrangement reaction of an oxime compound with no generation of large amounts of by-products such as ammonium sulfate to thereby produce an amide or lactam in a high yield and a simple method.
- Another object of the present invention is to provide a process that smoothly allows a rearrangement reaction of an oxime compound with a catalyst and a cocatalyst, both of which will be easily removed after the completion of reaction, to thereby produce an amide or lactam with a high degree of purification in a simple method.
- the present inventors After intensive investigations to achieve the above objects, the present inventors have found that the objects are achieved by the combination of a cyclic compound, containing a specific structure as a ring constituent, with a fluorinated alcohol.
- the present invention has been made based on these findings.
- the present invention provides a process for the production of amides or lactams, which process includes the step of carrying out a rearrangement of an oxime compound in the presence of a fluorinated alcohol and a cyclic compound containing a structure represented by following Formula (1) as a ring constituent to yield a corresponding amide or lactam:
- Z represents a halogen atom or an —OR group, where R represents an organic group.
- Z is preferably chlorine atom.
- Exemplary preferred fluorinated alcohols include fluorine-containing branched-chain aliphatic alcohols represented by following Formula 3):
- Rf 1 and Rf 2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- the organic group R is preferably a fluorine-containing branched-chain aliphatic group represented by following Formula (3a):
- Rf 1 and Rf 2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- Exemplary oxime compounds include oxime compounds each represented by following Formula (4) or (5):
- R a and R b each independently represent an organic group, and one of R a and R b may be hydrogen atom,
- m denotes an integer of 2 or more.
- the organic group R is preferably a group corresponding to the oxime compound and represented by following Formula (4a) or (5a):
- R a and R b each independently represent an organic group, and one of R a and R b may be hydrogen atom,
- amides or lactams can be simply or easily produced in high yields while eliminating problems on removal or disposal of by-products generated in known processes for the production of amides or lactams, because rearrangement reactions of oximes can be carried out without generation of large amounts of by-products such as ammonium sulfate.
- fluorinated alcohol as a cocatalyst helps to accelerate the reaction and to reduce the amount of catalysts.
- the fluorinated alcohol is easily separable from a product after the completion of the reaction and helps to save time and effort for purifying the product to thereby simply produce an amide or lactam with a high degree of purification.
- a cyclic compound containing a structure represented by following Formula (1) as a ring constituent is used as a catalyst, and a fluorinated alcohol is coexisted, so that a rearrangement reaction of an oxime compound rapidly and efficiently proceed to thereby give a corresponding amide or lactam in a high yield:
- Z represents a halogen atom or an OR group, where R represents an organic group.
- halogen atoms as Z in Formula (1) include fluorine atom, chlorine atom, bromine atom, and iodine atom, of which chlorine atom is preferred.
- the organic group as R in Formula (1) is not particularly limited, but it is preferably, for example, a group represented by following Formula (2), an alkyl group, or a haloalkyl group:
- R s and R t are the same as or different from each other and each represent a hydrocarbon group, and R s and R t may be combined to form a nonaromatic ring with the carbon atom to which R s and R t are bound.
- Exemplary hydrocarbon groups as R s and R t include, but are not limited to, aliphatic chain groups, such as alkyl groups having about one to ten carbon atoms, alkenyl groups, and alkynyl groups; as well as cycloalkyl groups, aryl groups, and aralkyl groups.
- An example of the nonaromatic ring formed by R s , R t and the carbon atom to which R t and R s are bound includes a cycloalkyl group.
- the group represented by Formula (2) is a cycloalkylideneamino group.
- the organic group R is a group represented by Formula (2)
- the group may be a group corresponding to the oxime compound used as a starting material. Namely, the group is represented by Chemical Formula in which —OH group is removed from the chemical formula of the corresponding oxime compound.
- Exemplary alkyl groups as R include straight- or branched-chain alkyl groups having one to ten carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl.
- Exemplary haloalkyl groups as R include groups corresponding to the alkyl groups, except with one or more halogen atoms, such as fluorine, chlorine, bromine, and iodine, being substituted.
- Preferred haloalkyl groups include fluorinated alkyl groups substituted with fluorine atom, of which fluorine-containing branched-chain aliphatic groups represented by Formula (3a) are more preferred.
- the group represented by R is a fluorinated alkyl group
- the fluorinated alkyl group is often a group corresponding to the fluorinated alcohol to be used:
- Rf 1 and Rf 2 may be the same as or different from each other and each represent a perfluoroalkyl group having about one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- Exemplary usable cyclic compounds containing the structure represented by Formula (1) as a ring constituent include, but are not limited to, aromatic cyclic compounds or nonaromatic cyclic compounds each containing one or more of the structure per molecule. Among them, aromatic cyclic compounds are preferably used herein as cyclic compounds containing the structure represented by Formula (1) as a ring constituent. Exemplary aromatic cyclic compounds include triazine derivatives represented by following Formula (1a), pyrazine derivatives represented by following Formula (1b), pyrimidine derivatives represented by following Formula (1c), pyridazine derivatives represented by following Formula (1d), and pyridine derivatives represented by following Formula (1e):
- Z represents a halogen atom or an —OR group;
- R represents an organic group;
- X 1 , X 2 , X 3 , and X 4 are the same as or different from one another and each represent hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group (such as trifluoromethyl group, difluoromethyl group, or trichloromethyl group), an aryl group, a cycloalkyl group, hydroxyl group, an alkoxy group, an aryloxy group, a haloalkoxy group, mercapto group, carboxyl group, a substituted oxycarbonyl group, formyl group, an acyl group, an acyloxy group, nitro group, sulfo group, cyano group, amino group, oxyamino group, or another organic group, and at least two of X 1 , X 2 , X 3 , and X 4
- Exemplary haloalkoxy groups as X 1 , X 2 , X 3 and X 4 include groups corresponding to fluorine-containing branched-chain aliphatic alcohols represented by Formula (3), such as hexafluoroisopropyloxy group (2,2,2-trifluoro-1-trifluoromethylethoxy group).
- the groups are represented by Chemical Formula in which hydrogen atom is removed from Formula (3) of the corresponding fluorine-containing branched-chain aliphatic alcohols.
- Exemplary haloalkoxy groups further include groups corresponding to fluorine-containing straight-chain aliphatic alcohols (fluorine-containing primary alcohols).
- the groups are represented by Chemical Formula in which hydrogen atom is removed from Formula (3) of the corresponding fluorine-containing straight-chain aliphatic alcohols.
- exemplary other organic groups as X 1 , X 2 , X 3 and X 4 include groups corresponding to the groups represented by Formula (2), except with oxygen atom bound to the nitrogen atom thereof.
- X 1 , X 2 , X 3 and X 4 in the compounds represented by Formulae (1a) to (1e) may be the same groups as Z, namely, they may be groups selected from halogen atoms and —OR groups.
- triazine derivatives represented by Formula (1a), in which X 1 and X 2 are groups selected from halogen atoms and —OR groups, are cyclic compounds containing three of the structure represented by Formula (1) per molecule.
- Pyrazine derivatives represented by Formula (1b), pyrimidine derivatives represented by Formula (1c), and pyridazine derivatives represented by Formula (1d), in which X 3 is a group selected from halogen atoms and —OR groups are cyclic compounds containing two of the structure represented by Formula (1) per molecule.
- exemplary triazine derivatives represented by Formula (1a) include triazine derivatives having one or more halogen atoms (typically chlorine atoms) as substituents, such as 2-chloro-1,3,5-triazine, 2,4-dichloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride), 2-chloro-4,6-dihydroxy-1,3,5-triazine, 2-chloro-4,6-dinitro-1,3,5-triazine, 2-chloro-4-nitro-1,3,5-triazine, and 2-chloro-4,6-dioxymethyl-1,3,5-triazine; triazine derivatives having one or more haloalkoxy groups as substituents, such as 2-hexafluoroisopropyloxy-1,3,5-triazine, 2,4-bis(hexafluoroisopropyloxy)-1,3,5-tritri
- Exemplary pyrazine derivatives represented by Formula (1b) include pyrazine derivatives having one or more halogen atoms as substituents, such as 2-chloropyrazine, 2,3-dichloropyrazine, and 2-chloro-3,5-dinitropyrazine; pyrazine derivatives having one or more haloalkoxy groups as substituents, such as 2-(hexafluoroisopropyloxy)pyrazine; and pyrazine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2-cyclododecylideneaminooxypyrazine.
- halogen atoms such as 2-chloropyrazine, 2,3-dichloropyrazine, and 2-chloro-3,5-dinitropyrazine
- pyrazine derivatives having one or more haloalkoxy groups as substituents such as 2-(hexafluoroiso
- Exemplary pyrimidine derivatives represented by Formula (1c) include pyrimidine derivatives-having one or more halogen atoms as substituents, such as 2,4-dichloro-pyrimidine, 2,4,6-trichloropyrimidine, 4,6-dichloro-5-nitropyrimidine, and 2,4-dichloro-6-nitropyrimidine; pyrimidine derivatives having one or more haloalkoxy groups as substituents, such as 2,4-bis(hexafluoroisopropyloxy)pyrimidine; and pyrimidine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2,4-dicyclododecylideneaminooxypyrimidine.
- halogen atoms such as 2,4-dichloro-pyrimidine, 2,4,6-trichloropyrimidine, 4,6-dichloro-5-nitropyrimidine, and 2,4-dichloro-6-nitropyrimidine
- Exemplary pyridazine derivatives represented by Formula (1d) include pyridazine derivatives having one or more halogen atoms as substituents, such as 3-chloropyridazine and 3,6-dichloropyridazine; pyridazine derivatives having one or more haloalkoxy groups as substituents, such as 3-hexafluoroisopropyloxypyridazine; and pyridazine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 3-cyclododecylideneaminooxypyridazine.
- Exemplary pyridine derivatives represented by Formula (1e) include pyridine derivatives having one or more halogen atoms as substituents, such as 2-chloro-3,5-dinitropyridine, 2,4,6-trichloropyridine, and 2-chloropyridine; pyridine derivatives having one or more haloalkoxy groups as substituents, such as 2-hexafluoroisopropyloxypyridine; and pyridine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2-cyclododecylideneaminooxypyridine.
- halogen atoms such as 2-chloro-3,5-dinitropyridine, 2,4,6-trichloropyridine, and 2-chloropyridine
- pyridine derivatives having one or more haloalkoxy groups as substituents such as 2-hexafluoroisopropyloxypyridine
- triazine derivatives represented by Formula (1a) are preferred, of which 2,4,6-trichloro-1,3,5-triazine, 2,4,6-tris(hexafluoroisopropyloxy)-1,3,5-triazine, and 2,4,6-tris(cyclododecylideneaminooxy)-1,3,5-triazine are more preferred.
- Exemplary cyclic compounds containing the structure represented by Formula (1) as a ring constituent further include compounds having a nitrogen-containing fused heterocyclic skeleton, such as quinoline, isoquinoline, quinazoline, quinoxaline, phthalazine, purine, pteridine, phenanthridine, and phenanthroline.
- Exemplary cyclic compounds further include aromatic or nonaromatic cyclic compounds containing at least one heteroatom other than nitrogen atom as a ring constituent and also containing the structure represented by Formula (1) as a ring constituent.
- the cyclic compound containing the structure represented by Formula (1) as a ring constituent is a compound having an —OR group as Z
- the cyclic compound may be prepared beforehand and subjected to a reaction.
- such a cyclic compound having an —OR group as Z is formed by incorporating a corresponding compound having a halogen atom as Z in combination with a compound that generates an RO ⁇ ion into a reaction system for the production of an amide or lactam and thereby allowing a substitution reaction between the halogen atom and the —OR group to proceed in the reaction system.
- the compound that generates an RO ⁇ ion is not particularly limited, but it is often a fluorinated alcohol used as a cocatalyst or an oxime compound used as a starting material herein.
- exemplary embodiments of the present invention in which Z is an —OR group further include an embodiment in which a cyclic compound containing the structure represented by Formula (1) as a ring constituent, in which Z is a halogen atom, is allowed to react with a fluorinated alcohol to give a cyclic compound having a haloalkoxy group as a substituent in situ in the reaction system; and an embodiment in which a cyclic compound containing the structure represented by Formula (1) as a ring constituent, in which Z is a halogen atom, is allowed to react with an oxime compound to give a cyclic compound having, as a substituent, a group corresponding to the oxime compound and represented by Chemical Formula in which hydrogen atom is removed from the chemical formula of the corresponding oxime compound (e
- the amount of the compound containing the structure represented by Formula (1) as a ring constituent is, for example, about 0.0001 to 1 mole, preferably about 0.0005 to 0.5 mole, and more preferably about 0.001 to 0.2 mole, per 1 mole of oxime compounds.
- Each of different compounds containing the structure represented by Formula (1) as a ring constituent can be used alone or in combination.
- Fluorinated alcohols for use herein are not particularly limited and include any aliphatic alcohols or aromatic alcohols with fluorine atom replacing part or all of hydrogen atoms of hydrocarbon moiety. Such fluorinated alcohols may be monohydric alcohols or polyhydric alcohols.
- Exemplary fluorinated aliphatic alcohols include aliphatic chain alcohols and aliphatic cyclic alcohols.
- Exemplary preferred aliphatic chain alcohols include fluorine-containing straight-chain aliphatic alcohols as straight-chain alcohols having about one to twenty carbon atoms with fluorine atom replacing part or all of hydrogen atoms of hydrocarbon moiety; and fluorine-containing branched-chain aliphatic alcohols having about three to twenty carbon atoms with fluorine atom replacing part or all of hydrogen atoms of hydrocarbon moiety.
- their hydrocarbon moieties hereinafter referred to as a “fluorinated hydrocarbon moieties” may contain one or more unsaturated bonds.
- Exemplary fluorine-containing straight-chain aliphatic alcohols with fluorine atom replacing part of hydrogen atoms of hydrocarbon moiety include 1,1-difluoroethanol, 1,1,2-trifluoroethanol, 2,2,2-trifluoroethanol, 1,1-difluoro-1-propanol, 1,2-difluoro-1-propanol, 1,2,3-trifluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 1,1,2,2-tetrafluoro-1-propanol, 1,3-difluoro-1,3-propanediol, 2,3,4-trifluoro-1-butanol, 4,4,4-trifluoro-1-butanol, 3,3,4,4,4-pentafluoro-1-butanol, 1,1,2,2,3,3-hexafluoro-1-butanol, 1,1,2,2-tetrafluoro-1-butanol, 1,2,3,4-tetraflu
- Exemplary fluorine-containing aliphatic branched-chain alcohols include hexafluoroisopropanol, heptafluoroisopropanol, 3,3,3-trifluoro-2-trifluoromethyl-1-propanol, 2-trifluoromethyl-1-butanol, 2-trifluoromethyl-1,4-butanediol, and 2-trifluoromethyl-3,3,4,4,4-pentafluoro-1-butanol.
- Exemplary fluorinated aliphatic cyclic alcohols usable herein include aliphatic cyclic alcohols having about three to twenty carbon atoms, such as cyclohexanol and cyclopentanol, with one or more fluorine atoms per molecule.
- the way to contain fluorine atoms is not particularly limited.
- fluorine atoms may be bound to a carbon atom constituting a ring; or a fluorine-containing hydrocarbon group may be bound to a carbon atom constituting a ring.
- Exemplary usable fluorinated aromatic alcohols include aromatic alcohols, such as benzyl alcohol and phenylethanol, with one or more fluorine atoms per molecule.
- the way to contain fluorine atoms is not particularly limited.
- a fluorinated hydrocarbon group may be substituted on an aromatic ring, or a chain hydrocarbon moiety may have a fluorine atom.
- fluorinated alcohols fluorine-containing branched-chain aliphatic alcohols represented by following Formula (3) are preferred, of which hexafluoroisopropanol is more preferred:
- Rf 1 and Rf 2 may be the same as or different from each other and each represent a perfluoroalkyl group having about one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- the fluorinated alcohol is a compound represented by Formula (3), and R in Formula (1) is a group represented by following Formula (3a):
- Rf 1 and Rf 2 may be the same as or different from each other and each represent a perfluoroalkyl group having about one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- the amount of fluorinated alcohols is not particularly limited and may be selected within a broad range of, for example, 0.001 mole or more, preferably 0.05 mole or more, and more preferably 0.5 mole or more, per 1 mole of oxime compounds.
- fluorinated alcohols are used in large excess to oxime compounds.
- fluorinated alcohols are used as solvents.
- Each of different fluorinated alcohols may be used alone or in combination.
- Oxime compounds for use herein as starting materials are not particularly limited and may be selected suitably according to an amide or lactam to be produced.
- Exemplary oxime compounds include compounds represented by following Formula (4) or Formula (5):
- R a and R b each independently represent an organic group, where one of R a and R b may be hydrogen atom,
- Organic groups as R a and R b include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, dodecyl, and pentadecyl groups, of which those having one to twenty carbon atoms are preferred, those having one to twelve carbon atoms are more preferred, and those having two to eight carbon atoms are further preferred; alkenyl groups such as vinyl, allyl, 1-propenyl, 1-butenyl, 1-pentenyl, and 1-octenyl groups, of which those having two to twenty carbon atoms are preferred, those having two to twelve carbon atoms are more preferred, and those having about two to eight carbon atoms are further preferred; alkynyl groups such as
- Each of these organic groups may have one or more substituents of every kind within ranges not adversely affecting the reaction.
- substituents include halogen atoms, oxo group, hydroxyl group, mercapto group, substituted oxy groups (e.g., alkoxy groups, aryloxy groups, and acyloxy groups), substituted thio groups, carboxyl group, substituted oxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyano group, nitro group, substituted or unsubstituted amino groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (e.g., phenyl and naphthyl groups), aralkyl groups, and heterocyclic groups.
- Exemplary oxime compounds represented by Formula (4) include acetaldehyde oxime, acetone oxime, 2-butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 1-cyclohexyl-1-propanone oxime, benzaldehyde oxime, acetophenone oxime, benzophenone oxime, and 4′-hydroxyacetophenone oxime.
- the ring in Formula (5) may have one or more substituents bound thereto, and/or may have one or more other rings fused thereto.
- “m” is, for example, about 2 to 30, preferably about 4 to 20, and more preferably about 5 to 14.
- Exemplary cyclic oxime compounds represented by Formula (5) include cyclopropanone oxime, cyclobutanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cyclododecanone oxime, cyclotridecanone oxime, cyclotetradecanone oxime, cyclopentadecanone oxime, cyclohexadecanone oxime, cyclooctadecanone oxime, and cyclononadecanone oxime.
- Exemplary substituents which may combine with the ring contain the above-exemplified substituents which the above-mentioned organic groups may have.
- the oxime compound is represented by Formula (4), and group R in Formula (1) is represented by following Formula (4a).
- the oxime compound is represented by Formula (5), and group R in Formula (1) is represented by following Formula (5a):
- R a and R b each independently represent an organic group, where one of R a and R b may be hydrogen atom.
- Each of different oxime compounds may be selected and used alone or in combination.
- Rearrangement reactions of oxime compounds are carried out in the presence of, or in the absence of solvents.
- the solvents may be the above-mentioned fluorinated alcohols or other solvents.
- the other solvents have only to be inert (inactive) under reaction conditions.
- Exemplary other solvents include organic acids such as acetic acid, propionic acid, and trifluoroacetic acid; nitrites such as acetonitrile, propionitrile, and benzonitrile; amides such as formamide, acetamide, dimethylformamide (DMF), and dimethylacetamide; aliphatic hydrocarbons such as hexane and octane; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane, and nitroethane; esters such as ethyl acetate and butyl acetate; and mixtures of these solvents.
- organic acids such as acetic acid, propionic acid, and trifluoroacetic acid
- nitrites such as acetonitrile, propionitrile, and
- a reaction temperature is not particularly limited and may be set according typically to the types of oxime compounds to be used, and the types of catalysts and solvents. It is, for example, about 0° C. to 250° C., preferably about 25° C. to 150° C., and more preferably about 40° C. to 120° C.
- a reaction may be carried out in an atmosphere of an inert gas such as nitrogen or argon gas, or can be carried out in an atmosphere of air or oxygen. Particularly, in a preferred embodiment of the present invention, the reaction is carried out in an air atmosphere under reflux conditions.
- an oxime compound represented by Formula (4) yields an amide compound represented by following Formula (6); and a cyclic oxime compound represented by Formula (5) yields a lactam represented by following Formula (7). More specifically, acetophenone oxime typically yields acetanilide; and a cycloalkanone oxime yields a lactam having one more number of members constituting a ring than the number of the members constituting a ring of original cycloalkanone oxime.
- cyclohexanone oxime yields ⁇ -caprolactam
- cycloheptanone oxime yields 7-heptanelactam
- cyclooctanone oxime yields 8-octanelactam
- Reaction products after the completion of reaction may be separated and purified by a separation procedure such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, or column chromatography, or any combination of these separation procedures.
- an oxime compound can be simply and efficiently prepared under mild conditions according to the following process. Further, the process is very advantageous because a reaction for the synthesis of the oxime compound and a reaction for the formation of an amide or lactam through rearrangement of the oxime compound can be carried out in one step without requiring an extra step of separating and purifying the oxime compound in the midway.
- an oxime compound is preferably prepared by reacting a compound having methyl group or methylene group with a nitrous ester or nitrite (salt of nitrous acid) in the presence of a nitrogen-containing cyclic compound containing, as a ring constituent, a skeleton represented by following Formula (8):
- Y represents an oxygen atom or an —OR′ group
- R′ represents hydrogen atom or a hydroxyl-protecting group
- Exemplary usable nitrogen-containing cyclic compounds containing the skeleton represented by Formula (8) as a ring constituent include N-hydroxyimide compounds derived from aliphatic polycarboxylic acid anhydrides (cyclic anhydrides) or aromatic polycarboxylic acid anhydrides (cyclic anhydrides), such as N-hydroxysuccinimide, N-hydroxyphthalimide, N,N′-dihydroxypyromellitic diimide, N-hydroxyglutarimide, N-hydroxy-1,8-naphthalenedicarboximide, N,N′-dihydroxy-1,8,4,5-naphthalenetetracarboxylic diimide; and compounds obtained by introducing a protecting group to the hydroxyl group of the corresponding N-hydroxyimide compounds.
- N-hydroxyimide compounds derived from aliphatic polycarboxylic acid anhydrides (cyclic anhydrides) or aromatic polycarboxylic acid anhydrides (cyclic anhydrides) such as N-hydroxysuccinimide, N-hydroxy
- Exemplary compounds having methyl group or methylene group include compounds represented by following Formula (9):
- R a and R b are as defined above.
- exemplary compounds having methyl group or methylene group include ethane, propane, butane, pentane, hexane, heptane, octane, n-propylcyclohexane, toluene, p-xylene, ethylbenzene, isopropylbenzene, diphenylmethane, and 1,2-diphenylethane.
- Exemplary compounds having methylene group further include compounds represented by following Formula (10):
- the ring in Formula (10) may have one or more substituents thereon and/or may have one or more other rings fused thereto.
- Exemplary compounds represented by Formula (10) include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cyclooctadecane, and cyclononadecane.
- the substituents which may bond to the ring are as with the above-exemplified substituents which the organic groups may have.
- the nitrous esters include alkyl nitrites such as methyl nitrite, ethyl nitrite, propyl nitrite, isopropyl nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, isoamyl nitrite, t-amyl nitrite, and hexyl nitrite; aryl nitrites such as phenyl nitrite; and aralkyl nitrites such as benzyl nitrite.
- alkyl nitrites such as methyl nitrite, ethyl nitrite, propyl nitrite, isopropyl nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, isoamyl nit
- Exemplary preferred nitrous esters include alkyl nitrites such as alkyl nitrites whose alkyl moiety has one to six carbon atoms.
- Exemplary nitrites salts of nitrous acid
- the ratio of a compound having methyl group or methylene group to a nitrous ester or nitrite may be suitably set according typically to the types and combination of the two compounds.
- the compound having methyl group or methylene group may be used in an equivalent amount or in excess (e.g., about 1.1 to 50 times by equivalent weight or more, and preferably about 3 to 30 times by equivalent weight) to the nitrous ester or nitrite; or conversely, the nitrous ester or nitrite may be used in excess to the compound having methyl group or methylene group.
- a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is carried out in the presence of, or in the absence of, a solvent.
- the solvent herein is not particularly limited, and exemplary solvents include the above-exemplified solvents usable in rearrangement reactions of oxime compounds.
- a reaction temperature and other conditions are not particularly limited, and the reaction can be carried out under conditions as in the rearrangement reactions of oxime compounds. Typically, the reaction temperature is about 0° C. to 250° C., preferably about 25° C. to 150° C., and more preferably about 40° C. to 120° C.
- the reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
- the reaction may be carried out in an atmosphere of air or oxygen.
- the reaction can be carried out under reduced pressure, under normal pressure, or under a pressure (under a load), according to a common system such as batch system, semi-batch system, or continuous system (e.g., a multistage continuous circulation system).
- the reaction is preferably conducted under reduced pressure and is more preferably under such reduced pressure as to remove nitrogen oxide gases (typified by NO 2 ) by-produced in the reaction, e.g., at about 30 to 700 mmHg (3.99 to 93.1 kPa). This gives remarkably improved yields. This is probably because nitrogen oxide gases such as NO 2 adversely affect the reaction.
- a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite initially gives a nitroso compound, and the nitroso compound undergoes rearrangement to give an oxime compound.
- a reaction between cyclohexane and a nitrous ester or nitrite initially gives nitrosocyclohexane, and this undergoes rearrangement to give cyclohexanone oxime.
- a nitroso compound of some type may be in equilibrium with a corresponding dimer (a di-N-oxide compound composed of two molecules of nitroso compound bonded through their nitrogen atoms), and the equilibrium may lie to the dimer.
- the nitroso compound and a dimer thereof can be in trace amounts and in yields of at most less than 1%.
- a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted by adding the nitrous ester or nitrite sequentially (intermittently) or continuously to the reaction system.
- side reactions typically in nitrosation are suppressed to give a nitroso compound or a dimer thereof with high selectivity, as compared in the case where the nitrous ester or nitrite is added all at once. Accordingly, a subsequent rearrangement reaction typically gives an oxime compound in a high yield.
- reactions may be conducted stepwise by arranging a step of carrying out a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite to give a nitroso compound or a dimer thereof, and a step of converting the formed nitroso compound or a dimer thereof into the oxime compound.
- the total reaction period may be significantly reduced or shortened by adding additives to the reaction system or by carrying out heating in the latter conversion step (nitroso compound rearrangement step).
- the former nitrosation step and the latter rearrangement step may be conducted in different solvents. According to this technic, the latter nitrosation step is preferably conducted under reduced pressure to increase the yield remarkably, for the same reason as above.
- the additives are not particularly limited, as long as they can induce a rearrangement from the nitroso form to the oxime form; and exemplary preferred additives include acids and bases.
- Exemplary acids include sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, and fuming sulfuric acid; Lewis acids such as aluminum chloride, zinc chloride, and scandium triflate; solid acids such as silica, alumina, and zeolite; complex acids including polyacids such as phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, and silicotungstic acid; and strongly acidic cation-exchange resins.
- Exemplary bases include organic bases including tertiary amines such as triethylamine, nitrogen-containing heterocyclic compounds such as pyridine, as well as sodium acetate and sodium methoxide; inorganic bases such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, and potassium hydroxide; and solid bases such as magnesium oxide, hydrotalcite, and hydroxyapatite.
- organic bases including tertiary amines such as triethylamine, nitrogen-containing heterocyclic compounds such as pyridine, as well as sodium acetate and sodium methoxide
- inorganic bases such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, and potassium hydroxide
- solid bases such as magnesium oxide, hydrotalcite, and hydroxyapatite.
- Such additives may be added all at once or in plural installments.
- the amount of additives is, for example, about 0.01 to 100 parts by weight, preferably about 0.1 to 50 parts by weight, and more preferably about 0.3 to 30 parts by weight
- a rearrangement reaction using additives may be conducted at temperatures of, for example, about 40° C. to 120° C., and preferably about 50° C. to 100° C. for a period of, for example, about 5 to 180 minutes, and preferably about 10 to 120 minutes.
- a rearrangement reaction by heating may be conducted at heating temperatures of, for example, about 120° C. to 250° C., and preferably about 150° C. to 200° C. for reaction periods of, for example, about 0.5 to 120 minutes, and preferably about 2 to 90 minutes.
- An amide or lactam can be prepared from a corresponding compound having methyl group or methylene group in one step by adding a cyclic compound which contains the structure represented by Formula (1) as a ring constituent and a fluorinated alcohol to the oxime producing reaction system including the compound having methyl group or methylene group, a nitrous ester or nitrite, and a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent.
- a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted in the presence of a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent and a cyclic compound which contains the structure represented by Formula (1) as a ring constituent to give an oxime compound, and then, a fluorinated alcohol is added after the formation of the oxime compound to carry out the rearrangement reaction of the oxime compound.
- a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted in the presence of a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent and a fluorinated alcohol to give an oxime compound, and then, a cyclic compound which contains the structure represented by Formula (1) as a ring constituent is added after the formation of the oxime compound to carry out the rearrangement reaction of the oxime compound.
- a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted in the presence of a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent to give an oxime compound, and then, a cyclic compound which contains the structure represented by Formula (1) as a ring constituent and a fluorinated alcohol are added to carry out the rearrangement reaction of the oxime compound.
- one or more procedures such as evaporation of solvents, concentration, and solvent exchange may be conducted at suitable periods.
- the formation of an oxime compound may be conducted stepwise as described above.
- the processes according to the present invention simply produce amides or lactams in high yields without causing large amounts of by-products. They also simply produce amides or lactams with high degrees of purification, because catalysts and other components used herein are easily separable from the produced amides or lactams. They further simply and efficiently produce amides or lactams, because the step of yielding an oxime from a starting material such as an aliphatic or aromatic hydrocarbon and the step of yielding an amide or lactam from the oxime compound can be conducted in one step or in one pot. Typically, ⁇ -caprolactam and ⁇ -laurolactam can be efficiently produced from cyclohexane and cyclododecane, respectively.
- the produced amides or lactams are usable as raw materials typically for pharmaceutical drugs, agricultural chemicals, dyestuffs, solvents, and explosives and as starting materials for polyamides (nylons) and are industrially very important.
- Cyclododecanone oxime (10 mmol), cyanuric chloride (0.5 percent by mole to cyclododecanone oxime), and hexafluoroisopropanol (5 ml) were placed in a reactor, followed by stirring under reflux conditions for 2 hours.
- a gas chromatographic analysis was conducted after the reaction to find that laurolactam was formed in a yield of 99%.
- cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen.
- the reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, and an acid-type ion-exchange resin (AMBERLYST 15DRY; 0.05 g) was added, followed by stirring at 70° C. for 1 hour.
- AMBERLYST 15DRY an acid-type ion-exchange resin
- Cyanuric chloride was added with 5 times, by equivalent weight to cyanuric chloride, of hexafluoroisopropanol and 3.5 times, by equivalent weight to cyanuric chloride, of triethylamine, and the mixture was stirred in THF at room temperature for 5 hours. After the reaction, the solvent was evaporated and removed, the residue was purified by column chromatography and thereby yielded 2,4,6-tris(hexafluoroisopropyloxy)-1,3,5-triazine.
- Cyclododecanone oxime (10 mmol), 2,4,6-tris(cyclododecylideneaminooxy)-1,3,5-triazine (O-4,6-bis(cyclododecylideneaminooxy)-1,3,5-triazin-2-ylcyclododecanone oxime) (0.5 percent by mole), and hexafluoroisopropanol (2 ml) were placed in a reactor, followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that laurolactam was formed in a yield of 99%.
- rearrangement reactions of oximes can be carried out without causing large amounts of by-products such as ammonium sulfate, to thereby solve problems on removal and disposal of by-products formed in known processes for the production of amides or lactams, and amides or lactams can be simply produced in high yields.
Abstract
An amide or lactam is produced by conducting a rearrangement of a corresponding oxime compound in the presence of a cyclic compound containing a structure represented by following Formula (1) as a ring constituent and a fluorinated alcohol:
wherein Z represents a halogen atom or an —OR group, where R represents an organic group.
Z is preferably chlorine atom. Exemplary fluorinated alcohols include fluorine-containing branched-chain aliphatic alcohols represented by following Formula (3):
wherein Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
According to this process, amides or lactams can be simply produced in high yields without causing large amounts of by-products.
Description
- The present invention relates to processes for the production of lactams or amides that are useful typically as raw materials for pharmaceutical drugs, agricultural chemicals, dyestuffs, polyamides and the like, or as solvents. More specifically, it relates to processes for producing the amides or lactams through rearrangement reactions of oxime compounds.
- Techniques for producing amides or lactams from corresponding oxime compounds as raw materials through “Beckmann rearrangement” are industrially very important. The production of these compounds has been conducted using a process of acting fuming sulfuric acid in a stoichiometric amount or more, and this process raises an issue of by-product of large amounts of ammonium sulfate to be treated.
- To avoid this problem, there has been proposed the use of an aromatic compound, such as 2,4,6-trichloro-1,3,5-triazine, having a halogeno group that acts as a leaving group and two or more electron-withdrawing groups, as a Beckmann rearrangement catalyst. The catalyst applies less load on the environment (Non-patent Document 1). According to this technique, however, products are not easily separated and purified, because the technique requires use of a large amount of the catalyst or addition of an inorganic salt such as zinc chloride as a cocatalyst, for smoothly proceeding the reaction and yielding a target amide or lactam in a high yield.
- [Non-patent Document 1] J. AM. CHEM. SOC. 2005, 127, 11240-11241
- An object of the present invention is to provide a process that allows a rearrangement reaction of an oxime compound with no generation of large amounts of by-products such as ammonium sulfate to thereby produce an amide or lactam in a high yield and a simple method.
- Another object of the present invention is to provide a process that smoothly allows a rearrangement reaction of an oxime compound with a catalyst and a cocatalyst, both of which will be easily removed after the completion of reaction, to thereby produce an amide or lactam with a high degree of purification in a simple method.
- After intensive investigations to achieve the above objects, the present inventors have found that the objects are achieved by the combination of a cyclic compound, containing a specific structure as a ring constituent, with a fluorinated alcohol. The present invention has been made based on these findings.
- Specifically, the present invention provides a process for the production of amides or lactams, which process includes the step of carrying out a rearrangement of an oxime compound in the presence of a fluorinated alcohol and a cyclic compound containing a structure represented by following Formula (1) as a ring constituent to yield a corresponding amide or lactam:
- In Formula (1), Z represents a halogen atom or an —OR group, where R represents an organic group.
- Z is preferably chlorine atom.
- Exemplary preferred fluorinated alcohols include fluorine-containing branched-chain aliphatic alcohols represented by following Formula 3):
- In Formula (3), Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- In the cyclic compound containing the structure represented by Formula (1) as a ring constituent, the organic group R is preferably a fluorine-containing branched-chain aliphatic group represented by following Formula (3a):
- In Formula (3a), Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- Exemplary oxime compounds include oxime compounds each represented by following Formula (4) or (5):
- In Formula (4), Ra and Rb each independently represent an organic group, and one of Ra and Rb may be hydrogen atom,
- In Formula (5), “m” denotes an integer of 2 or more.
- In the cyclic compound containing the structure represented by Formula (1) as a ring constituent, the organic group R is preferably a group corresponding to the oxime compound and represented by following Formula (4a) or (5a):
- In Formula (4a), Ra and Rb each independently represent an organic group, and one of Ra and Rb may be hydrogen atom,
- In Formula (5a), “m” denotes an integer of 2 or more.
- According to the present invention, amides or lactams can be simply or easily produced in high yields while eliminating problems on removal or disposal of by-products generated in known processes for the production of amides or lactams, because rearrangement reactions of oximes can be carried out without generation of large amounts of by-products such as ammonium sulfate.
- Use of a fluorinated alcohol as a cocatalyst helps to accelerate the reaction and to reduce the amount of catalysts. The fluorinated alcohol is easily separable from a product after the completion of the reaction and helps to save time and effort for purifying the product to thereby simply produce an amide or lactam with a high degree of purification.
- According to the present invention, a cyclic compound containing a structure represented by following Formula (1) as a ring constituent is used as a catalyst, and a fluorinated alcohol is coexisted, so that a rearrangement reaction of an oxime compound rapidly and efficiently proceed to thereby give a corresponding amide or lactam in a high yield:
- In Formula (1), Z represents a halogen atom or an OR group, where R represents an organic group.
- Exemplary halogen atoms as Z in Formula (1) include fluorine atom, chlorine atom, bromine atom, and iodine atom, of which chlorine atom is preferred. The organic group as R in Formula (1) is not particularly limited, but it is preferably, for example, a group represented by following Formula (2), an alkyl group, or a haloalkyl group:
- In Formula (2), Rs and Rt are the same as or different from each other and each represent a hydrocarbon group, and Rs and Rt may be combined to form a nonaromatic ring with the carbon atom to which Rs and Rt are bound.
- Exemplary hydrocarbon groups as Rs and Rt include, but are not limited to, aliphatic chain groups, such as alkyl groups having about one to ten carbon atoms, alkenyl groups, and alkynyl groups; as well as cycloalkyl groups, aryl groups, and aralkyl groups. An example of the nonaromatic ring formed by Rs, Rt and the carbon atom to which Rt and Rs are bound includes a cycloalkyl group. In this case, the group represented by Formula (2) is a cycloalkylideneamino group. When the organic group R is a group represented by Formula (2), the group may be a group corresponding to the oxime compound used as a starting material. Namely, the group is represented by Chemical Formula in which —OH group is removed from the chemical formula of the corresponding oxime compound.
- Exemplary alkyl groups as R include straight- or branched-chain alkyl groups having one to ten carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl. Exemplary haloalkyl groups as R include groups corresponding to the alkyl groups, except with one or more halogen atoms, such as fluorine, chlorine, bromine, and iodine, being substituted. Preferred haloalkyl groups include fluorinated alkyl groups substituted with fluorine atom, of which fluorine-containing branched-chain aliphatic groups represented by Formula (3a) are more preferred. When the group represented by R is a fluorinated alkyl group, the fluorinated alkyl group is often a group corresponding to the fluorinated alcohol to be used:
- In Formula (3a), Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having about one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- Exemplary usable cyclic compounds containing the structure represented by Formula (1) as a ring constituent include, but are not limited to, aromatic cyclic compounds or nonaromatic cyclic compounds each containing one or more of the structure per molecule. Among them, aromatic cyclic compounds are preferably used herein as cyclic compounds containing the structure represented by Formula (1) as a ring constituent. Exemplary aromatic cyclic compounds include triazine derivatives represented by following Formula (1a), pyrazine derivatives represented by following Formula (1b), pyrimidine derivatives represented by following Formula (1c), pyridazine derivatives represented by following Formula (1d), and pyridine derivatives represented by following Formula (1e):
- In Formulae (1a) to (1e), Z represents a halogen atom or an —OR group; R represents an organic group; X1, X2, X3, and X4 are the same as or different from one another and each represent hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group (such as trifluoromethyl group, difluoromethyl group, or trichloromethyl group), an aryl group, a cycloalkyl group, hydroxyl group, an alkoxy group, an aryloxy group, a haloalkoxy group, mercapto group, carboxyl group, a substituted oxycarbonyl group, formyl group, an acyl group, an acyloxy group, nitro group, sulfo group, cyano group, amino group, oxyamino group, or another organic group, and at least two of X1, X2, X3, and X4 may be combined to form an aromatic or nonaromatic ring with atoms constituting the ring in the formulae.
- Exemplary haloalkoxy groups as X1, X2, X3 and X4 include groups corresponding to fluorine-containing branched-chain aliphatic alcohols represented by Formula (3), such as hexafluoroisopropyloxy group (2,2,2-trifluoro-1-trifluoromethylethoxy group). The groups are represented by Chemical Formula in which hydrogen atom is removed from Formula (3) of the corresponding fluorine-containing branched-chain aliphatic alcohols. Exemplary haloalkoxy groups further include groups corresponding to fluorine-containing straight-chain aliphatic alcohols (fluorine-containing primary alcohols). The groups are represented by Chemical Formula in which hydrogen atom is removed from Formula (3) of the corresponding fluorine-containing straight-chain aliphatic alcohols. Exemplary other organic groups as X1, X2, X3 and X4 include groups corresponding to the groups represented by Formula (2), except with oxygen atom bound to the nitrogen atom thereof. X1, X2, X3 and X4 in the compounds represented by Formulae (1a) to (1e) may be the same groups as Z, namely, they may be groups selected from halogen atoms and —OR groups. Typically, triazine derivatives represented by Formula (1a), in which X1 and X2 are groups selected from halogen atoms and —OR groups, are cyclic compounds containing three of the structure represented by Formula (1) per molecule. Pyrazine derivatives represented by Formula (1b), pyrimidine derivatives represented by Formula (1c), and pyridazine derivatives represented by Formula (1d), in which X3 is a group selected from halogen atoms and —OR groups, are cyclic compounds containing two of the structure represented by Formula (1) per molecule.
- More specifically, exemplary triazine derivatives represented by Formula (1a) include triazine derivatives having one or more halogen atoms (typically chlorine atoms) as substituents, such as 2-chloro-1,3,5-triazine, 2,4-dichloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride), 2-chloro-4,6-dihydroxy-1,3,5-triazine, 2-chloro-4,6-dinitro-1,3,5-triazine, 2-chloro-4-nitro-1,3,5-triazine, and 2-chloro-4,6-dioxymethyl-1,3,5-triazine; triazine derivatives having one or more haloalkoxy groups as substituents, such as 2-hexafluoroisopropyloxy-1,3,5-triazine, 2,4-bis(hexafluoroisopropyloxy)-1,3,5-triazine, and 2,4,6-tris(hexafluoroisopropyloxy)-1,3,5-triazine; triazine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2-cyclohexylideneaminooxy-1,3,5-triazine, 2-cyclododecylideneaminooxy-1,3,5-triazine, 2,4-bis(cyclohexylideneaminooxy)-1,3,5-triazine, 2,4-bis(cyclododecylideneaminooxy)-1,3,5-triazine, 2,4,6-tris(cyclohexylideneaminooxy)-1,3,5-triazine, and 2,4,6-tris(cyclododecylideneaminooxy)-1,3,5-triazine; triazine derivatives having at least one halogen atom and at least one haloalkoxy group as substituents, such as 2-chloro-4,6-bis(hexafluoroisopropyloxy)-1,3,5-triazine and 2,4-dichloro-6-(hexafluoroisopropyloxy)-1,3,5-triazine; triazine derivatives having at least one halogen atom and at least one cycloalkylideneaminooxy group as substituents, such as 2-chloro-4-cyclohexylideneaminooxy-1,3,5-triazine and 2-chloro-4-cyclododecylideneaminooxy-1,3,5-triazine; triazine derivatives having at least one cycloalkylideneaminooxy group and at least one haloalkoxy group as substituents, such as 2-cyclohexylideneaminooxy-4,6-bis(hexafluoroisopropyloxy)-1,3,5-triazine and 2-cyclododecylideneaminooxy-4,6-bis(hexafluoroisopropyloxy)-1,3,5-triazine; and triazine derivatives having at least one halogen atom, at least one haloalkoxy group, and at least one cycloalkylideneamino group as substituents, such as 2-chloro-4-(hexafluoroisopropyloxy)-6-cyclohexylideneaminooxy-1,3,5-triazine and 2-chloro-4-(hexafluoroisopropyloxy)-6-cyclododecylideneaminooxy-1,3,5-triazine.
- Exemplary pyrazine derivatives represented by Formula (1b) include pyrazine derivatives having one or more halogen atoms as substituents, such as 2-chloropyrazine, 2,3-dichloropyrazine, and 2-chloro-3,5-dinitropyrazine; pyrazine derivatives having one or more haloalkoxy groups as substituents, such as 2-(hexafluoroisopropyloxy)pyrazine; and pyrazine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2-cyclododecylideneaminooxypyrazine.
- Exemplary pyrimidine derivatives represented by Formula (1c) include pyrimidine derivatives-having one or more halogen atoms as substituents, such as 2,4-dichloro-pyrimidine, 2,4,6-trichloropyrimidine, 4,6-dichloro-5-nitropyrimidine, and 2,4-dichloro-6-nitropyrimidine; pyrimidine derivatives having one or more haloalkoxy groups as substituents, such as 2,4-bis(hexafluoroisopropyloxy)pyrimidine; and pyrimidine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2,4-dicyclododecylideneaminooxypyrimidine.
- Exemplary pyridazine derivatives represented by Formula (1d) include pyridazine derivatives having one or more halogen atoms as substituents, such as 3-chloropyridazine and 3,6-dichloropyridazine; pyridazine derivatives having one or more haloalkoxy groups as substituents, such as 3-hexafluoroisopropyloxypyridazine; and pyridazine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 3-cyclododecylideneaminooxypyridazine.
- Exemplary pyridine derivatives represented by Formula (1e) include pyridine derivatives having one or more halogen atoms as substituents, such as 2-chloro-3,5-dinitropyridine, 2,4,6-trichloropyridine, and 2-chloropyridine; pyridine derivatives having one or more haloalkoxy groups as substituents, such as 2-hexafluoroisopropyloxypyridine; and pyridine derivatives having one or more cycloalkylideneaminooxy groups as substituents, such as 2-cyclododecylideneaminooxypyridine.
- Among them, triazine derivatives represented by Formula (1a) are preferred, of which 2,4,6-trichloro-1,3,5-triazine, 2,4,6-tris(hexafluoroisopropyloxy)-1,3,5-triazine, and 2,4,6-tris(cyclododecylideneaminooxy)-1,3,5-triazine are more preferred.
- Exemplary cyclic compounds containing the structure represented by Formula (1) as a ring constituent further include compounds having a nitrogen-containing fused heterocyclic skeleton, such as quinoline, isoquinoline, quinazoline, quinoxaline, phthalazine, purine, pteridine, phenanthridine, and phenanthroline. Exemplary cyclic compounds further include aromatic or nonaromatic cyclic compounds containing at least one heteroatom other than nitrogen atom as a ring constituent and also containing the structure represented by Formula (1) as a ring constituent.
- When the cyclic compound containing the structure represented by Formula (1) as a ring constituent is a compound having an —OR group as Z, the cyclic compound may be prepared beforehand and subjected to a reaction. In another embodiment, such a cyclic compound having an —OR group as Z is formed by incorporating a corresponding compound having a halogen atom as Z in combination with a compound that generates an RO− ion into a reaction system for the production of an amide or lactam and thereby allowing a substitution reaction between the halogen atom and the —OR group to proceed in the reaction system. The compound that generates an RO− ion is not particularly limited, but it is often a fluorinated alcohol used as a cocatalyst or an oxime compound used as a starting material herein. Specifically, exemplary embodiments of the present invention in which Z is an —OR group further include an embodiment in which a cyclic compound containing the structure represented by Formula (1) as a ring constituent, in which Z is a halogen atom, is allowed to react with a fluorinated alcohol to give a cyclic compound having a haloalkoxy group as a substituent in situ in the reaction system; and an embodiment in which a cyclic compound containing the structure represented by Formula (1) as a ring constituent, in which Z is a halogen atom, is allowed to react with an oxime compound to give a cyclic compound having, as a substituent, a group corresponding to the oxime compound and represented by Chemical Formula in which hydrogen atom is removed from the chemical formula of the corresponding oxime compound (e.g., a cycloalkylideneaminooxy group).
- The amount of the compound containing the structure represented by Formula (1) as a ring constituent is, for example, about 0.0001 to 1 mole, preferably about 0.0005 to 0.5 mole, and more preferably about 0.001 to 0.2 mole, per 1 mole of oxime compounds. Each of different compounds containing the structure represented by Formula (1) as a ring constituent can be used alone or in combination.
- Fluorinated alcohols for use herein are not particularly limited and include any aliphatic alcohols or aromatic alcohols with fluorine atom replacing part or all of hydrogen atoms of hydrocarbon moiety. Such fluorinated alcohols may be monohydric alcohols or polyhydric alcohols.
- Exemplary fluorinated aliphatic alcohols include aliphatic chain alcohols and aliphatic cyclic alcohols. Exemplary preferred aliphatic chain alcohols include fluorine-containing straight-chain aliphatic alcohols as straight-chain alcohols having about one to twenty carbon atoms with fluorine atom replacing part or all of hydrogen atoms of hydrocarbon moiety; and fluorine-containing branched-chain aliphatic alcohols having about three to twenty carbon atoms with fluorine atom replacing part or all of hydrogen atoms of hydrocarbon moiety. In fluorinated aliphatic chain alcohols, their hydrocarbon moieties (hereinafter referred to as a “fluorinated hydrocarbon moieties”) may contain one or more unsaturated bonds. Exemplary fluorine-containing straight-chain aliphatic alcohols with fluorine atom replacing part of hydrogen atoms of hydrocarbon moiety include 1,1-difluoroethanol, 1,1,2-trifluoroethanol, 2,2,2-trifluoroethanol, 1,1-difluoro-1-propanol, 1,2-difluoro-1-propanol, 1,2,3-trifluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 1,1,2,2-tetrafluoro-1-propanol, 1,3-difluoro-1,3-propanediol, 2,3,4-trifluoro-1-butanol, 4,4,4-trifluoro-1-butanol, 3,3,4,4,4-pentafluoro-1-butanol, 1,1,2,2,3,3-hexafluoro-1-butanol, 1,1,2,2-tetrafluoro-1-butanol, 1,2,3,4-tetrafluoro-1-butanol, 3,3,4,4,4-pentafluoro-1-butanol, 1,2,3,4-tetrafluoro-1,4-butanediol, 1,1,2,2-tetrafluoro-1-pentanol, 5,5,5-trifluoro-1-pentanol, 4,4,5,5,5-pentafluoro-1-pentanol, 1,1,2,2-tetrafluoro-1-hexanol, and 5,5,6,6,6-pentafluoro-1-hexanol. Exemplary fluorine-containing aliphatic branched-chain alcohols include hexafluoroisopropanol, heptafluoroisopropanol, 3,3,3-trifluoro-2-trifluoromethyl-1-propanol, 2-trifluoromethyl-1-butanol, 2-trifluoromethyl-1,4-butanediol, and 2-trifluoromethyl-3,3,4,4,4-pentafluoro-1-butanol.
- Exemplary fluorinated aliphatic cyclic alcohols usable herein include aliphatic cyclic alcohols having about three to twenty carbon atoms, such as cyclohexanol and cyclopentanol, with one or more fluorine atoms per molecule. The way to contain fluorine atoms is not particularly limited. Typically, fluorine atoms may be bound to a carbon atom constituting a ring; or a fluorine-containing hydrocarbon group may be bound to a carbon atom constituting a ring.
- Exemplary usable fluorinated aromatic alcohols include aromatic alcohols, such as benzyl alcohol and phenylethanol, with one or more fluorine atoms per molecule. The way to contain fluorine atoms is not particularly limited. Typically, a fluorinated hydrocarbon group may be substituted on an aromatic ring, or a chain hydrocarbon moiety may have a fluorine atom.
- Among these fluorinated alcohols, fluorine-containing branched-chain aliphatic alcohols represented by following Formula (3) are preferred, of which hexafluoroisopropanol is more preferred:
- wherein Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having about one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- In a preferred embodiment of the present invention, the fluorinated alcohol is a compound represented by Formula (3), and R in Formula (1) is a group represented by following Formula (3a):
- wherein Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having about one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
- The amount of fluorinated alcohols is not particularly limited and may be selected within a broad range of, for example, 0.001 mole or more, preferably 0.05 mole or more, and more preferably 0.5 mole or more, per 1 mole of oxime compounds. In an embodiment, fluorinated alcohols are used in large excess to oxime compounds. In another preferred embodiment, fluorinated alcohols are used as solvents. Each of different fluorinated alcohols may be used alone or in combination.
- Oxime compounds for use herein as starting materials are not particularly limited and may be selected suitably according to an amide or lactam to be produced. Exemplary oxime compounds include compounds represented by following Formula (4) or Formula (5):
- wherein Ra and Rb each independently represent an organic group, where one of Ra and Rb may be hydrogen atom,
- wherein “m” denotes an integer of 2 or more.
- Organic groups as Ra and Rb include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, dodecyl, and pentadecyl groups, of which those having one to twenty carbon atoms are preferred, those having one to twelve carbon atoms are more preferred, and those having two to eight carbon atoms are further preferred; alkenyl groups such as vinyl, allyl, 1-propenyl, 1-butenyl, 1-pentenyl, and 1-octenyl groups, of which those having two to twenty carbon atoms are preferred, those having two to twelve carbon atoms are more preferred, and those having about two to eight carbon atoms are further preferred; alkynyl groups such as ethynyl and 1-propynyl groups, of which those having two to twenty carbon atoms are preferred, those having two to twelve carbon atoms are more preferred, and those having about two to eight carbon atoms are further preferred; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclododecyl groups, of which those having three to twenty carbon atoms are preferred, and those having three to fifteen carbon atoms are more preferred; cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cyclooctenyl groups, of which those having three to twenty carbon atoms are preferred, and those having three to fifteen carbon atoms are more preferred; aryl groups such as phenyl and naphthyl groups; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl groups; and aromatic or nonaromatic heterocyclic groups such as 2-pyridyl, 2-quinolyl, 2-furyl, 2-thienyl, and 4-piperidinyl groups. Each of these organic groups may have one or more substituents of every kind within ranges not adversely affecting the reaction. Exemplary substituents include halogen atoms, oxo group, hydroxyl group, mercapto group, substituted oxy groups (e.g., alkoxy groups, aryloxy groups, and acyloxy groups), substituted thio groups, carboxyl group, substituted oxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyano group, nitro group, substituted or unsubstituted amino groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (e.g., phenyl and naphthyl groups), aralkyl groups, and heterocyclic groups.
- Exemplary oxime compounds represented by Formula (4) include acetaldehyde oxime, acetone oxime, 2-butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 1-cyclohexyl-1-propanone oxime, benzaldehyde oxime, acetophenone oxime, benzophenone oxime, and 4′-hydroxyacetophenone oxime.
- The ring in Formula (5) may have one or more substituents bound thereto, and/or may have one or more other rings fused thereto. In Formula (5), “m” is, for example, about 2 to 30, preferably about 4 to 20, and more preferably about 5 to 14. Exemplary cyclic oxime compounds represented by Formula (5) include cyclopropanone oxime, cyclobutanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cyclododecanone oxime, cyclotridecanone oxime, cyclotetradecanone oxime, cyclopentadecanone oxime, cyclohexadecanone oxime, cyclooctadecanone oxime, and cyclononadecanone oxime. Exemplary substituents which may combine with the ring contain the above-exemplified substituents which the above-mentioned organic groups may have.
- In a preferred embodiment of the present invention, the oxime compound is represented by Formula (4), and group R in Formula (1) is represented by following Formula (4a). In another preferred embodiment, the oxime compound is represented by Formula (5), and group R in Formula (1) is represented by following Formula (5a):
- In Formula (4a), Ra and Rb each independently represent an organic group, where one of Ra and Rb may be hydrogen atom.
- In Formula (5a), “m” denotes an integer of 2 or more.
- Each of different oxime compounds may be selected and used alone or in combination.
- Rearrangement reactions of oxime compounds are carried out in the presence of, or in the absence of solvents. The solvents may be the above-mentioned fluorinated alcohols or other solvents. The other solvents have only to be inert (inactive) under reaction conditions. Exemplary other solvents include organic acids such as acetic acid, propionic acid, and trifluoroacetic acid; nitrites such as acetonitrile, propionitrile, and benzonitrile; amides such as formamide, acetamide, dimethylformamide (DMF), and dimethylacetamide; aliphatic hydrocarbons such as hexane and octane; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane, and nitroethane; esters such as ethyl acetate and butyl acetate; and mixtures of these solvents.
- A reaction temperature is not particularly limited and may be set according typically to the types of oxime compounds to be used, and the types of catalysts and solvents. It is, for example, about 0° C. to 250° C., preferably about 25° C. to 150° C., and more preferably about 40° C. to 120° C. A reaction may be carried out in an atmosphere of an inert gas such as nitrogen or argon gas, or can be carried out in an atmosphere of air or oxygen. Particularly, in a preferred embodiment of the present invention, the reaction is carried out in an air atmosphere under reflux conditions.
- By using the process according to the present invention, an oxime compound represented by Formula (4) yields an amide compound represented by following Formula (6); and a cyclic oxime compound represented by Formula (5) yields a lactam represented by following Formula (7). More specifically, acetophenone oxime typically yields acetanilide; and a cycloalkanone oxime yields a lactam having one more number of members constituting a ring than the number of the members constituting a ring of original cycloalkanone oxime. Typically, cyclohexanone oxime yields ε-caprolactam; cycloheptanone oxime yields 7-heptanelactam; and cyclooctanone oxime yields 8-octanelactam:
- wherein “m” is as defined above.
- Reaction products after the completion of reaction may be separated and purified by a separation procedure such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, or column chromatography, or any combination of these separation procedures.
- In a preferred embodiment, an oxime compound can be simply and efficiently prepared under mild conditions according to the following process. Further, the process is very advantageous because a reaction for the synthesis of the oxime compound and a reaction for the formation of an amide or lactam through rearrangement of the oxime compound can be carried out in one step without requiring an extra step of separating and purifying the oxime compound in the midway.
- Specifically, an oxime compound is preferably prepared by reacting a compound having methyl group or methylene group with a nitrous ester or nitrite (salt of nitrous acid) in the presence of a nitrogen-containing cyclic compound containing, as a ring constituent, a skeleton represented by following Formula (8):
- In Formula (8), Y represents an oxygen atom or an —OR′ group, and R′ represents hydrogen atom or a hydroxyl-protecting group.
- Exemplary usable nitrogen-containing cyclic compounds containing the skeleton represented by Formula (8) as a ring constituent include N-hydroxyimide compounds derived from aliphatic polycarboxylic acid anhydrides (cyclic anhydrides) or aromatic polycarboxylic acid anhydrides (cyclic anhydrides), such as N-hydroxysuccinimide, N-hydroxyphthalimide, N,N′-dihydroxypyromellitic diimide, N-hydroxyglutarimide, N-hydroxy-1,8-naphthalenedicarboximide, N,N′-dihydroxy-1,8,4,5-naphthalenetetracarboxylic diimide; and compounds obtained by introducing a protecting group to the hydroxyl group of the corresponding N-hydroxyimide compounds.
- Exemplary compounds having methyl group or methylene group include compounds represented by following Formula (9):
-
Ra—CH2—Rb(9) [Chemical Formula 21] - wherein Ra and Rb are as defined above.
- Specifically, exemplary compounds having methyl group or methylene group include ethane, propane, butane, pentane, hexane, heptane, octane, n-propylcyclohexane, toluene, p-xylene, ethylbenzene, isopropylbenzene, diphenylmethane, and 1,2-diphenylethane.
- Exemplary compounds having methylene group further include compounds represented by following Formula (10):
- wherein “m” is as defined above.
- The ring in Formula (10) may have one or more substituents thereon and/or may have one or more other rings fused thereto. Exemplary compounds represented by Formula (10) include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cyclooctadecane, and cyclononadecane. The substituents which may bond to the ring are as with the above-exemplified substituents which the organic groups may have.
- The nitrous esters include alkyl nitrites such as methyl nitrite, ethyl nitrite, propyl nitrite, isopropyl nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, isoamyl nitrite, t-amyl nitrite, and hexyl nitrite; aryl nitrites such as phenyl nitrite; and aralkyl nitrites such as benzyl nitrite. Exemplary preferred nitrous esters include alkyl nitrites such as alkyl nitrites whose alkyl moiety has one to six carbon atoms. Exemplary nitrites (salts of nitrous acid) include ammonium nitrite; alkaline earth metal salts of nitrous acid, such as lithium nitrite, sodium nitrite, potassium nitrite, and barium nitrite; and other metal salts of nitrous acid, such as zinc nitrite.
- The ratio of a compound having methyl group or methylene group to a nitrous ester or nitrite may be suitably set according typically to the types and combination of the two compounds. Typically, the compound having methyl group or methylene group may be used in an equivalent amount or in excess (e.g., about 1.1 to 50 times by equivalent weight or more, and preferably about 3 to 30 times by equivalent weight) to the nitrous ester or nitrite; or conversely, the nitrous ester or nitrite may be used in excess to the compound having methyl group or methylene group.
- A reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is carried out in the presence of, or in the absence of, a solvent. The solvent herein is not particularly limited, and exemplary solvents include the above-exemplified solvents usable in rearrangement reactions of oxime compounds. A reaction temperature and other conditions are not particularly limited, and the reaction can be carried out under conditions as in the rearrangement reactions of oxime compounds. Typically, the reaction temperature is about 0° C. to 250° C., preferably about 25° C. to 150° C., and more preferably about 40° C. to 120° C. The reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas. In some types of target products, the reaction may be carried out in an atmosphere of air or oxygen. The reaction can be carried out under reduced pressure, under normal pressure, or under a pressure (under a load), according to a common system such as batch system, semi-batch system, or continuous system (e.g., a multistage continuous circulation system). The reaction is preferably conducted under reduced pressure and is more preferably under such reduced pressure as to remove nitrogen oxide gases (typified by NO2) by-produced in the reaction, e.g., at about 30 to 700 mmHg (3.99 to 93.1 kPa). This gives remarkably improved yields. This is probably because nitrogen oxide gases such as NO2 adversely affect the reaction.
- It is supposed that a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite initially gives a nitroso compound, and the nitroso compound undergoes rearrangement to give an oxime compound. Typically, it is supposed that a reaction between cyclohexane and a nitrous ester or nitrite initially gives nitrosocyclohexane, and this undergoes rearrangement to give cyclohexanone oxime. A nitroso compound of some type may be in equilibrium with a corresponding dimer (a di-N-oxide compound composed of two molecules of nitroso compound bonded through their nitrogen atoms), and the equilibrium may lie to the dimer. When the reaction is conducted for a long period of time, the nitroso compound and a dimer thereof can be in trace amounts and in yields of at most less than 1%.
- In a preferred embodiment, a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted by adding the nitrous ester or nitrite sequentially (intermittently) or continuously to the reaction system. According to this technique, side reactions typically in nitrosation are suppressed to give a nitroso compound or a dimer thereof with high selectivity, as compared in the case where the nitrous ester or nitrite is added all at once. Accordingly, a subsequent rearrangement reaction typically gives an oxime compound in a high yield.
- In another embodiment for forming an oxime compound in a high yield, reactions may be conducted stepwise by arranging a step of carrying out a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite to give a nitroso compound or a dimer thereof, and a step of converting the formed nitroso compound or a dimer thereof into the oxime compound. When this technique is employed, the total reaction period may be significantly reduced or shortened by adding additives to the reaction system or by carrying out heating in the latter conversion step (nitroso compound rearrangement step). The former nitrosation step and the latter rearrangement step may be conducted in different solvents. According to this technic, the latter nitrosation step is preferably conducted under reduced pressure to increase the yield remarkably, for the same reason as above.
- The additives are not particularly limited, as long as they can induce a rearrangement from the nitroso form to the oxime form; and exemplary preferred additives include acids and bases. Exemplary acids include sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, and fuming sulfuric acid; Lewis acids such as aluminum chloride, zinc chloride, and scandium triflate; solid acids such as silica, alumina, and zeolite; complex acids including polyacids such as phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, and silicotungstic acid; and strongly acidic cation-exchange resins. Exemplary bases include organic bases including tertiary amines such as triethylamine, nitrogen-containing heterocyclic compounds such as pyridine, as well as sodium acetate and sodium methoxide; inorganic bases such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, and potassium hydroxide; and solid bases such as magnesium oxide, hydrotalcite, and hydroxyapatite. Such additives may be added all at once or in plural installments. The amount of additives is, for example, about 0.01 to 100 parts by weight, preferably about 0.1 to 50 parts by weight, and more preferably about 0.3 to 30 parts by weight, to 100 parts by weight of the compound having methyl group or methylene group. A rearrangement reaction using additives may be conducted at temperatures of, for example, about 40° C. to 120° C., and preferably about 50° C. to 100° C. for a period of, for example, about 5 to 180 minutes, and preferably about 10 to 120 minutes. A rearrangement reaction by heating may be conducted at heating temperatures of, for example, about 120° C. to 250° C., and preferably about 150° C. to 200° C. for reaction periods of, for example, about 0.5 to 120 minutes, and preferably about 2 to 90 minutes.
- An amide or lactam can be prepared from a corresponding compound having methyl group or methylene group in one step by adding a cyclic compound which contains the structure represented by Formula (1) as a ring constituent and a fluorinated alcohol to the oxime producing reaction system including the compound having methyl group or methylene group, a nitrous ester or nitrite, and a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent. In another embodiment, a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted in the presence of a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent and a cyclic compound which contains the structure represented by Formula (1) as a ring constituent to give an oxime compound, and then, a fluorinated alcohol is added after the formation of the oxime compound to carry out the rearrangement reaction of the oxime compound. In still another embodiment, a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted in the presence of a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent and a fluorinated alcohol to give an oxime compound, and then, a cyclic compound which contains the structure represented by Formula (1) as a ring constituent is added after the formation of the oxime compound to carry out the rearrangement reaction of the oxime compound. In yet another embodiment, a reaction between a compound having methyl group or methylene group and a nitrous ester or nitrite is conducted in the presence of a nitrogen-containing cyclic compound which contains the skeleton represented by Formula (8) as a ring constituent to give an oxime compound, and then, a cyclic compound which contains the structure represented by Formula (1) as a ring constituent and a fluorinated alcohol are added to carry out the rearrangement reaction of the oxime compound. In these techniques, one or more procedures such as evaporation of solvents, concentration, and solvent exchange may be conducted at suitable periods. The formation of an oxime compound may be conducted stepwise as described above.
- The processes according to the present invention simply produce amides or lactams in high yields without causing large amounts of by-products. They also simply produce amides or lactams with high degrees of purification, because catalysts and other components used herein are easily separable from the produced amides or lactams. They further simply and efficiently produce amides or lactams, because the step of yielding an oxime from a starting material such as an aliphatic or aromatic hydrocarbon and the step of yielding an amide or lactam from the oxime compound can be conducted in one step or in one pot. Typically, ε-caprolactam and ω-laurolactam can be efficiently produced from cyclohexane and cyclododecane, respectively.
- The produced amides or lactams are usable as raw materials typically for pharmaceutical drugs, agricultural chemicals, dyestuffs, solvents, and explosives and as starting materials for polyamides (nylons) and are industrially very important.
- The present invention will be illustrated in further detail with reference to several examples below, which, however, are by no means intended to limit the scope of the present invention.
- Cyclododecanone oxime (10 mmol), cyanuric chloride (0.5 percent by mole to cyclododecanone oxime), and hexafluoroisopropanol (5 ml) were placed in a reactor, followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that laurolactam was formed in a yield of 99%.
- Cyclohexanone oxime (10 mmol), cyanuric chloride (10 percent by mole to cyclohexanone oxime), and hexafluoroisopropanol (5 ml) were placed in a reactor, followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that caprolactam and a compound represented by following Formula (11) were formed in yields of 58% and 27%, respectively.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a flask, followed by stirring at 75° C. in an argon atmosphere (1 atm=0.101 MPa) for 2 hours. After the reaction, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with triethylamine (0.5 g) and ethyl acetate (1 ml), followed by stirring at 70° C. for 1 hour. Thereafter ethyl acetate and triethylamine were evaporated and removed, the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 1.3 mmol of caprolactam was formed.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with triethylamine (0.5 g) and ethyl acetate (1 ml), followed by stirring at 70° C. for 1 hour. Thereafter ethyl acetate and triethylamine were evaporated and removed, the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 2.1 mmol of caprolactam was formed.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a flask, followed by stirring at 75° C. under reduced pressure [600 mmHg (79.8 kPa)] for 2 hours. After the reaction, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with triethylamine (0.5 g) and ethyl acetate (1 ml), followed by stirring at 70° C. for 1 hour. Thereafter ethyl acetate and triethylamine were evaporated and removed, the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 2.0 mmol of caprolactam was formed.
- Cyclohexane (4 ml), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a flask, and t-butyl nitrite (4 mmol) was added dropwise thereto at 75° C. under reduced pressure [600 mmHg (79.8 kPa)] over 2 hours for a reaction. After the reaction, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with triethylamine (0.5 g) and ethyl acetate (1 ml), followed by stirring at 70° C. for 1 hour. Thereafter ethyl acetate and triethylamine were evaporated and removed, and the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 2.1 mmol of caprolactam was formed.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with triethylamine (0.5 g), followed by stirring at 70° C. for 1 hour. Thereafter triethylamine was evaporated and removed, and the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 1.9 mmol of caprolactam was formed.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, and sulfuric acid (0.05 g) was added, followed by stirring at 70° C. for 1 hour. Thereafter cyclohexane and acetic acid were evaporated and removed, and the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 1.8 mmol of caprolactam was formed.
- cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, and an acid-type ion-exchange resin (AMBERLYST 15DRY; 0.05 g) was added, followed by stirring at 70° C. for 1 hour. After filtration, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 1.9 mmol of caprolactam was formed.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a pressure-tight glass reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, and the mixture was heated to 180° C., followed by heating at this temperature for 1 hour. Thereafter cyclohexane and acetic acid were evaporated and removed, and the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 1.5 mmol of caprolactam was formed.
- Cyclohexane (4 ml), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. Thereafter the reduced pressure was released to normal pressure, hexafluoroisopropanol (2 ml) and cyanuric chloride (0.2 mmol) were added, followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 1.8 mmol of caprolactam was formed.
- Cyclododecane (3 g), t-butyl nitrite (4 mmol), N-hydroxyphthalimide (0.2 mmol), and acetic acid (0.5 ml) were placed in a reactor, and the resulting solution was frozen. The reactor was evacuated, adjusted in pressure to 50 mmHg (6.65 kPa) with argon gas, and sealed, followed by stirring at 75° C. for 2 hours. After the reaction, the reduced pressure was released to normal pressure, cyclohexane and acetic acid were evaporated and removed, and the residue was combined with triethylamine (0.5 g) and ethyl acetate (1 ml), followed by stirring at 70° C. for 1 hour. Thereafter ethyl acetate and triethylamine were evaporated and removed, and the residue was combined with hexafluoroisopropanol (2 ml) and cyanuric chloride (0.02 mmol), followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that 2.9 mmol of laurolactam was formed.
- Cyanuric chloride was added with 5 times, by equivalent weight to cyanuric chloride, of hexafluoroisopropanol and 3.5 times, by equivalent weight to cyanuric chloride, of triethylamine, and the mixture was stirred in THF at room temperature for 5 hours. After the reaction, the solvent was evaporated and removed, the residue was purified by column chromatography and thereby yielded 2,4,6-tris(hexafluoroisopropyloxy)-1,3,5-triazine.
- Cyclododecanone oxime (10 mmol), 2,4,6-tris(hexafluoroisopropyloxy)-1,3,5-triazine (2,4,6-tris(2,2,2-trifluoro-1-trifluoromethylethoxy)-1,3,5-triazine) (0.5 percent by mole), and hexafluoroisopropanol (2 ml) were placed in a reactor, followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that laurolactam was formed in a yield of 99%.
- Cyclododecanone oxime (10 mmol), 2,4,6-tris(cyclododecylideneaminooxy)-1,3,5-triazine (O-4,6-bis(cyclododecylideneaminooxy)-1,3,5-triazin-2-ylcyclododecanone oxime) (0.5 percent by mole), and hexafluoroisopropanol (2 ml) were placed in a reactor, followed by stirring under reflux conditions for 2 hours. A gas chromatographic analysis was conducted after the reaction to find that laurolactam was formed in a yield of 99%.
- According to the present invention, rearrangement reactions of oximes can be carried out without causing large amounts of by-products such as ammonium sulfate, to thereby solve problems on removal and disposal of by-products formed in known processes for the production of amides or lactams, and amides or lactams can be simply produced in high yields.
Claims (6)
1. A process for the production of amides or lactams, comprising the step of carrying out a rearrangement of an oxime compound in the presence of a fluorinated alcohol and a cyclic compound containing a structure represented by following Formula (1) as a ring constituent to yield a corresponding amide or lactam:
wherein Z represents a halogen atom or an —OR group, where R represents an organic group.
2. The process for the production of amides or lactams of claim 1 , wherein Z is chlorine atom.
3. The process for the production of amides or lactams of claim 1 , wherein the fluorinated alcohol is a fluorine-containing branched-chain aliphatic alcohol represented by following Formula (3):
wherein Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
4. The process for the production of amides or lactams of claim 3 , wherein R in Formula (1) is a fluorine-containing branched-chain aliphatic group represented by following Formula (3a):
wherein Rf1 and Rf2 may be the same as or different from each other and each represent a perfluoroalkyl group having one to eight carbon atoms; and “n” denotes an integer of 0 to 8.
6. The process for the production of amides or lactams of claim 5 , wherein R in Formula (1) is a group corresponding to the oxime compound and represented by following Formula (4a) or (5a):
wherein Ra and Rb each independently represent an organic group, where one of Ra and Rb may be hydrogen atom,
wherein “m” denotes an integer of 2 or more.
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JP2008156277A (en) * | 2006-12-22 | 2008-07-10 | Daicel Chem Ind Ltd | Method for producing lactam compound |
WO2008096873A1 (en) * | 2007-02-09 | 2008-08-14 | National University Corporation Nagoya University | Method for production of laurolactam |
US8309714B2 (en) | 2007-11-29 | 2012-11-13 | Ube Industries, Ltd. | Process for producing laurolactam |
JP5467725B2 (en) * | 2008-02-08 | 2014-04-09 | 国立大学法人名古屋大学 | Method for producing cyclic lactam compound and Beckmann rearrangement catalyst |
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US5886152A (en) * | 1991-12-06 | 1999-03-23 | Sumitomo Pharmaceuticals Company, Limited | Humanized B-B10 |
US20020123657A1 (en) * | 2000-10-24 | 2002-09-05 | Banks Ronald Eric | Electrophilic fluorination |
US20030176723A1 (en) * | 2000-03-29 | 2003-09-18 | Patrick Bernadelli | Modifying chemoselectivity during oxidation of nitrogen compounds |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4029159B2 (en) * | 2005-01-14 | 2008-01-09 | 国立大学法人名古屋大学 | Catalyst for Beckmann rearrangement reaction of oxime compound and method for producing amide compound using the same |
-
2006
- 2006-09-08 JP JP2006244862A patent/JP2007284415A/en not_active Withdrawn
-
2007
- 2007-02-27 WO PCT/JP2007/053578 patent/WO2007105482A1/en active Application Filing
- 2007-02-27 US US12/224,660 patent/US20090093628A1/en not_active Abandoned
- 2007-02-27 EP EP07714971A patent/EP2006283A2/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5886152A (en) * | 1991-12-06 | 1999-03-23 | Sumitomo Pharmaceuticals Company, Limited | Humanized B-B10 |
US20030176723A1 (en) * | 2000-03-29 | 2003-09-18 | Patrick Bernadelli | Modifying chemoselectivity during oxidation of nitrogen compounds |
US20020123657A1 (en) * | 2000-10-24 | 2002-09-05 | Banks Ronald Eric | Electrophilic fluorination |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110065913A1 (en) * | 2008-05-20 | 2011-03-17 | Ube Industries, Ltd. | Process for producing laurolactam |
US8338589B2 (en) | 2008-05-20 | 2012-12-25 | Ube Industries, Ltd. | Process for producing laurolactam |
Also Published As
Publication number | Publication date |
---|---|
EP2006283A2 (en) | 2008-12-24 |
JP2007284415A (en) | 2007-11-01 |
EP2006283A9 (en) | 2009-07-15 |
WO2007105482A1 (en) | 2007-09-20 |
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